JP3592668B2 - Food preservation method and unfrozen water production method - Google Patents
Food preservation method and unfrozen water production method Download PDFInfo
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- JP3592668B2 JP3592668B2 JP2001380369A JP2001380369A JP3592668B2 JP 3592668 B2 JP3592668 B2 JP 3592668B2 JP 2001380369 A JP2001380369 A JP 2001380369A JP 2001380369 A JP2001380369 A JP 2001380369A JP 3592668 B2 JP3592668 B2 JP 3592668B2
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/06—Freezing; Subsequent thawing; Cooling
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/06—Freezing; Subsequent thawing; Cooling
- A23B4/066—Freezing; Subsequent thawing; Cooling the materials not being transported through or in the apparatus with or without shaping, e.g. in the form of powder, granules or flakes
- A23B4/068—Freezing; Subsequent thawing; Cooling the materials not being transported through or in the apparatus with or without shaping, e.g. in the form of powder, granules or flakes with packages or with shaping in the form of blocks or portions
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/10—Coating with a protective layer; Compositions or apparatus therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/04—Freezing; Subsequent thawing; Cooling
- A23B7/0425—Freezing; Subsequent thawing; Cooling the material not being transported through or in the apparatus, with or without shaping, e.g. in the form of powder, granules or flakes
- A23B7/0433—Freezing; Subsequent thawing; Cooling the material not being transported through or in the apparatus, with or without shaping, e.g. in the form of powder, granules or flakes with packages or with shaping in the form of blocks or portions
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C19/00—Cheese; Cheese preparations; Making thereof
- A23C19/097—Preservation
- A23C19/0976—Freezing; Treating cheese in frozen state; Thawing of frozen cheese
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C3/00—Preservation of milk or milk preparations
- A23C3/04—Preservation of milk or milk preparations by freezing or cooling
- A23C3/05—Preservation of milk or milk preparations by freezing or cooling in packages
- A23C3/055—Freezing in packages
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
- A23G9/04—Production of frozen sweets, e.g. ice-cream
- A23G9/08—Batch production
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
- A23L3/363—Freezing; Subsequent thawing; Cooling the materials not being transported through or in the apparatus with or without shaping, e.g. in form of powder, granules, or flakes
- A23L3/364—Freezing; Subsequent thawing; Cooling the materials not being transported through or in the apparatus with or without shaping, e.g. in form of powder, granules, or flakes with packages or with shaping in form of blocks or portions
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
- A23L3/37—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
- A23L3/375—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals with direct contact between the food and the chemical, e.g. liquid nitrogen, at cryogenic temperature
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Nutrition Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Dairy Products (AREA)
- Freezing, Cooling And Drying Of Foods (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、食品を過冷却状態で保存する方法、食品を凍結状態で保存する方法、および水を過冷却状態として未凍結水を製造する方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
食品の保存方法としての低温保存は一般的に実施されている方法であり、また有効な方法であることは周知の事実である。低温保存の技術は、冷蔵と冷凍に大きく分けることができ、微生物学的には保存温度が低いほど有利であることもよく知られている。
しかしながら、冷凍による保存方法では、凍結によるドリップの発生、蛋白質変性、細胞組織の損傷や変形による肉質の損傷など、冷凍障害と言われる品質の劣化が生じ易いのが問題であった。
【０００３】
ところで、食品を特定の冷却条件で冷却していくと、該食品の凍結点以下の温度でも凍っていない状態、すなわち過冷却状態となることが知られており、このような過冷却状態で食品を保存すると、凍結による蛋白質変性、細胞組織の損傷などの冷却障害を回避できる利点がある。
【０００４】
食品を過冷却状態で保存するための方法として、例えば、特開平５−１６１４４９号公報には、果実・野菜を厚さ２０〜１００μｍのプラスチック製袋に密封して、１分〜１２時間で、当該果実・野菜の氷結点（凍結点）よりも１〜２℃高い温度まで冷却した後、−０．５℃／時間〜−０．５／２４時間の非常に緩慢な冷却速度で過冷却破壊温度の手前の温度まで冷却し、そのまま貯蔵または輸送する方法が記載されている。
また特開平８−２５２０８２号公報には、食品を、常温から氷結点（凍結点）付近まで急速に冷却し、続いて氷結点以下まで、０．０１℃／時間〜０．５／時間の緩慢な冷却速度で冷却することによって過冷却状態とする方法が記載されている。
【０００５】
しかしながら、これらの方法は食品を過冷却状態とするために、緩慢な冷却を行う必要があるため、冷却工程に時間がかかって処理能力が低いうえ、冷却過程での細菌の増殖を十分に抑えることが難しいという問題があった。
【０００６】
また、過冷却状態は、相転移温度以下に冷却されても、液体や蒸気に転移が起こらず元の相を保っている状態であり、非常に不安定な状態である。このため、不純物の混入、振動、温度変化によって極めて容易に過冷却状態が解除されて、食品が凍結してしまうので、食品を保存する方法として実用性に欠けるという問題があった。
【０００７】
さらに、水道水など不純物が含まれている水は、凍結点以下で安定した未凍結状態とするのは難しく、前記特開平８−２５２０８２号公報には、原料水をミクロフィルター等により濾過および／または蒸留することによって不純物を除去する工程を経て、未凍結水を製造する方法が記載されている。
【０００８】
しかしながら、このように原料水中の不純物を除去する工程を設けると、製造工程が複雑化し、生産性も悪くなり、製造コストが高くなってしまうという問題があった。
【０００９】
本発明は前記事情に鑑みてなされたもので、食品をより短時間で過冷却状態とすることができ、しかも過冷却状態を安定して維持できる食品の保存方法を提供することを目的とする。
また本発明は、食品を品質の劣化が少ない凍結状態で保存できる食品の保存方法を提供することを目的とする。
また本発明は、未凍結水を、簡単な工程により、低コストで製造できる未凍結水の製造方法を提供することを目的とする。
【００１０】
【課題を解決するための手段】
本発明者等は、食品を過冷却状態とするための冷却条件について鋭意研究した結果、食品を容器内にヘッドスペースが無いように収容した状態とすることによって、従来、過冷却状態を得るのに必要とされていた緩慢な冷却速度よりも、速い冷却速度で冷却しても食品を凍結させずに過冷却状態とすることができること、およびこのように食品を容器内にヘッドスペースが無いように収容した状態で従来よりも速い冷却速度で過冷却状態とした食品は、過冷却状態の安定性に優れていることを見出した。
【００１１】
すなわち本発明の食品の保存方法は、食品を過冷却状態で保存する方法であって、食品を、容器内にヘッドスペースが無いように収容した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て、該食品を過冷却状態とすることを特徴とする。前記容器としては、プラスチックを含む材料、特に、ナイロン、ポリエチレン、ポリスチレン、ポリプロピレン、およびポリエチレンテレフタレートからなる群から選ばれる少なくとも一種を含む材料からなるものが好適である。
【００１２】
また本発明者等は、さらに研究を重ねた結果、本発明の方法により過冷却状態とした食品に、強制的に刺激を与えて過冷却状態を解除すると、食品が急速に凍結すること、およびこのようにして得られた凍結状態は、過冷却状態を通過してしまう従来の急速凍結法に比べて細胞組織の損傷が少なく、品質の劣化が極めて小さいことを知見した。
【００１３】
すなわち本発明の食品の保存方法は、食品を凍結状態で保存する方法であって、食品を、容器内にヘッドスペースが無いように収容した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て該食品を過冷却状態とした後、該過冷却状態を解除して凍結状態とすることを特徴とする。
【００１４】
前記過冷却状態を解除するために、−１５℃／ｈ以上の冷却速度で冷却することが好ましい。
【００１５】
さらに、本発明に係る方法によれば、水を簡単に、安定した過冷却状態とすることができる。
すなわち本発明の未凍結水の製造方法は、水を、容器内にヘッドスペースが無いように充填した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て、該水を未凍結水とすることを特徴とする。
【００１６】
【発明の実施の形態】
以下、本発明を詳しく説明する。まず、本発明の第１の実施形態として食品を過冷却状態で保存する方法について説明する。
本実施形態においては、まず、食品を容器内に収容して密封する。このとき容器内にヘッドスペース（気相）がない状態とする。
食品は特に制限されるものでなく、液状、ペースト状、固形状の各種の食品が適用可能である。例えば、飲用水、原料水、牛乳、その他の飲料、クリーム、練乳、ヨーグルト、チーズ、その他の乳製品、果実、野菜、肉類、魚介類、各種加工食品等が挙げられる。
食品が液状またはペースト状である場合は、例えば容器内に食品を充填して液面下シールすることにより、容易にヘッドスペースをなくすことができる。一方、食品が固形状である場合は、容器内に食品を収容するとともに、例えば水、溶液、牛乳など食品の品質に悪影響を与えない液体を充填し、液面下シールすることにより、ヘッドスペースをなくすことができる。
【００１７】
容器は、例えば、ステンレスやガラスなど硬質の材料からなるものよりも、プラスチックフィルムや、プラスチックフィルムを備えた複合材料など柔軟性のある材料からなるものの方が、過冷却状態を安定的に得られるので好ましい。例えば、後記実施例におけるモッツァレラチーズの場合には、実施例に記載されたモッツァレラチーズをステンレス缶に充填し（ヘッドスペースなし）、実施例と同様の冷却を行えば、凍結する確率は各実施例よりも高くなるのである。
好ましい容器の材料は、プラスチックを含む材料であり、ナイロン、ポリエチレン、ポリスチレン、ポリプロピレン、ポリエチレンテレフタレート等から選ばれるいずれかのプラスチック材料、これらから選ばれる２種以上のプラスチック材料をラミネート等により組み合わせた複合材料、これらから選ばれる１種以上のプラスチック材料と紙などのその他の材料を組み合わせた複合材料等が挙げられる。プラスチック材料とその他の材料とを組み合わせた場合、容器の内面（即ち食品に接する側の面）がプラスチック材料で形成されていることが好ましい。容器の形状は特に限定されないが、例えば袋状、球状、チューブ状、スタンディングパウチ状等とすることできるが、可及的に球状に近いほうが好ましい。
【００１８】
次に、食品を容器内に収容したものを冷却し、食品の温度を該食品が過冷却状態となる過冷却領域まで低下させる。冷却条件は、食品の温度が低下する過程で、少なくとも凍結点を通過する際の冷却速度が−０．５℃／ｈを越え−５．０℃／ｈ以下の範囲内、すなわち−０．５℃／ｈより速く−５．０℃／ｈまたはこれより遅い速度となるように設定する。
凍結点を通過する際の冷却速度が上記の範囲より遅いと、細菌の増殖を抑える効果が十分に得られず処理効率も悪くなる。また冷却速度が上記の範囲よりも速いと過冷却状態が得られないことがある。
【００１９】
容器内に、固形状の食品とヘッドスペースをなくすための液体が収容されている場合には、食品および液体の両方が過冷却状態となる温度まで冷却する。またこの場合の冷却条件は、食品および液体の温度が低下する過程で、食品の凍結点を通過する際の冷却速度、および液体の凍結点を通過する際の冷却速度の両方が−０．５℃／ｈを越え−５．０℃／ｈ以下の範囲内となるように設定する。
冷却は、例えば、冷却し始めてから所望の過冷却領域に至るまで−０．５℃／ｈを越え−５．０℃／ｈ以下の一定の冷却速度で一段階で冷却してもよく、あるいは冷却しはじめてから凍結点付近までは−５．０℃／ｈを越える冷却速度で第１の冷却を行い、続いて冷却速度を−０．５℃／ｈを越え−５．０℃／ｈ以下の範囲内に低減させて凍結点以下の過冷却領域まで第２の冷却を行ってもよい。
冷却中は、食品が収容された容器を静置状態とすることが好ましい。例えば、所定の温度に設定された冷蔵庫内に食品が収容された容器を静置保管することによって冷却を行うことが好ましく、冷蔵庫内の設定温度や、庫内における冷風流量、冷風の当たりかたや、庫内の有効容積を変えることによって冷却速度を制御することができる。
【００２０】
このようにして過冷却状態とした食品を、容器ごと過冷却領域の温度に維持することによって、食品を過冷却状態で保存することができる。
食品の凍結点および過冷却領域の温度帯は個々の食品毎にほぼ決まっており、過冷却領域の温度帯は、原則として凍結点から、凍結点より−２０℃低い温度までの温度範囲である。なお、凍結点の例と、特に好ましい過冷却領域の範囲があるものについては、その領域の例を下記表１に示す。
【００２１】
【表１】
本実施形態によれば、食品の品温を低下させる過程において、−０．５℃／ｈを越え−５．０℃／ｈ以下という従来よりも速い冷却速度で、該食品の凍結点を通過させることができるので、従来よりも短時間で食品を過冷却状態とすることができる。したがって、冷却工程に要する時間を短縮することができ、処理能力の向上を図ることができる。
また設備的には従来の冷却設備を用いることができ、新たな設備を設けなくて済む。また、過冷却状態を得るのに食品に添加物を加えたり、圧力を与えたりするものではないので、食品の風味を損うおそれがなく、風味が変化し易い乳飲料類や乳製品等にも適用することができる。
【００２３】
また製造された食品を、より短時間で過冷却状態とすることができるので、製造後の初期段階での細菌の増殖を効果的に抑えることができる。したがって、特に、比較的細菌が増殖し易い、乳飲料類や乳製品等の保存に好適であり、保存性を向上させることができる。
また、食品を容器内にヘッドスペースが無いように収容した状態で、比較的速い冷却速度で冷却することにより過冷却状態とされた食品は、容易に過冷却状態が破壊されず、安定した過冷却状態を維持することができる。したがって、振動が加わっても凍結状態となり難いので、過冷却領域の温度帯での輸送が可能であり、輸送後も良好な過冷却状態を保つことができる。
【００２４】
次に、本発明の第２の実施形態として食品を凍結状態で保存する方法について説明する。
本実施形態おいては、まず前記第１の実施形態と同様に、食品を容器内にヘッドスペースが無いように収容した状態で、少なくとも凍結点を通過する際の冷却速度が−０．５℃／ｈを越え−５．０℃／ｈ以下の範囲内となる冷却条件で、食品の温度を過冷却領域まで低下させる。
次に、このようにして過冷却状態とした食品に対して、強制的に刺激を与えることにより過冷却状態を解除して食品を凍結状態とする。具体的には、過冷却状態にある容器入り食品を−１５℃／ｈ以上の冷却速度で冷却することが好ましい。このときの冷却速度が−１５℃／ｈよりも小さいと、凍結過程で細胞組織の破壊や蛋白質の変性が生じるおそれがある。
【００２５】
このようにして凍結状態とした食品を、容器ごと凍結点よりも低温に維持することによって、食品を凍結状態で保存することができる。
【００２６】
本実施形態によれば、前記第１の実施形態と同様にして、凍結点以下の温度で水分が凍結していない過冷却状態とした後、急速に凍結させることにより、冷凍障害の少ない凍結状態を得ることがができる。これは、過冷却状態で細胞内液および細胞外液が凍結していない状態から、急速に凍結させることにより、凍結過程で細胞内液から細胞外液へ自由水の移行が生じ、細胞外液は希釈されて凍結し易く、細胞内液は濃縮されて凍結し難くなった結果、細胞内液のみが未凍結で他は凍結された状態が得られるためと考えられる。また、蛋白質を含む食品の場合、急速に凍結させることによって氷結晶が小さくなるため蛋白質の三次構造が氷結晶によって破壊されることが少なくなり、蛋白質の変性が抑制される。
また、食品を比較的短時間で過冷却領域にまで冷却するので、製造後の初期段階での細菌の増殖を効果的に抑えて、保存性の向上を図ることができる。
【００２７】
本実施形態の方法は、前記第１の実施形態と同様に各種の食品に適用可能であり、冷凍障害を防止して品質を高度に維持しつつ冷凍保存することができる。特に、従来は冷凍障害が生じ易いとされていた果実類や野菜類、および比較的水分の多い乳製品についても、凍結保存および解凍による品質劣化を防止することができるので好適である。
【００２８】
例えば従来の凍結技術では、いかに急速に凍結し、いわゆる最大氷結晶生成帯を短時間に通過させて氷晶を微粒化できるかを技術開発の焦点としていたが、この方法のみでは限界があった。すなわち、例えばイチゴのような元々軟弱な果実や、モッツァレラチーズ、クリームチーズ等の水分の多い乳製品などは、いかに急速に凍結したとしても凍結により組織が破壊され、離水が生じ商品価値を失ってしまうことが避けられなかった。
これに対して、本実施形態の方法によれば、例えば野菜や果実、乳製品など冷凍障害が生じやすい食品にあっても、凍結過程および解凍過程における組織の破壊を防止することができ、凍結前の組織状態を維持することができる。
【００２９】
次に、本発明の第３の実施形態として未凍結水を製造する方法について説明する。
本実施形態においては、まず前記第１の実施形態と同様にして、水を容器内に収容して密封する。このとき容器内にヘッドスペース（気相）がない状態とする。
水の組成は特に制限されない。通常の水道水でもよく、殺菌処理、不純物の除去処理等が施されたものでもよい。容器は、前記第１の実施形態と同様のものが使用できる。
次いで、水を容器内に充填したものを冷却し、前記第１の実施形態と同様に、少なくとも凍結点を通過する際の冷却速度が−０．５℃／ｈを越え−５．０℃／ｈ以下の範囲内となる冷却条件で、水の温度を過冷却領域まで低下させることにより、凍結点以下の温度で未凍結水を得る。
【００３０】
本実施形態によれば、水道水など不純物が含まれている水であっても、冷却工程を経るだけで簡単に過冷却状態とすることができるので、未凍結水を生産性良く、低コストで製造することができる。
【００３１】
【実施例】
以下、具体的な例を示して本発明の効果を明らかにする。
（例１〜例１０）
下記表２および表３に示す条件で、食品を容器内に収容し、所定の冷却速度で冷却した。
すなわち、容器としては、ナイロン／ポリエチレンの積層体からなる、サイズが１３．０ｃｍ×１４．５ｃｍの容器（大日本印刷社製）を用いた。
この容器に▲１▼水道水２１０ｇ、または▲２▼モッツァレラチーズ１００ｇと充填水１１０ｇ（表ではＭチーズと記載する）を充填した。
これを▲１▼液面下でヘッドスペースが無い状態でヒートシールして密封した（ヘッドスペース無し）、または▲２▼ヘッドスペースが無い状態でヒートシールした後に注射器を用いて容器内に空気を注入した（ヘッドスペース有り）。
このようにして食品が容器内に充填されたサンプルをそれぞれ２５個作製し、これらを２０℃の恒温室内に、容器内の品温が２０℃になるまで放置した後、所定の庫内温度に設定した恒温恒湿槽（ＬＨ４０−０３Ｍ：商品名、ナガノ科学機械製作所）内にて静置保管した。
容器内の食品の品温が低下する過程で、０℃付近を通過するときの冷却速度は、▲１▼−３．４℃／ｈ、▲２▼−１．９℃／ｈ、▲３▼−５．０℃／ｈ、または▲４▼−３．５℃／ｈとした。なお、冷却速度は必ずしも庫内温度と相関するわけではなく、庫内における冷風流量、冷風の当たりかたや、庫内の有効容積によって変動する。
例１〜例７では、恒温恒湿槽での保管を開始してから３日目以降、凍結が生じたサンプルの数を毎日調べた。例８〜１０では、恒温恒湿槽での保管を開始してから１５時間後、２４時間後、３９時間後、４８時間後、６３時間後、および８７時間後に凍結が生じたサンプルの数を調べた。これらの結果を表２および表３に示す。
【００３２】
【表２】
【表３】
表２の結果より、ヘッドスペース無しとした例２，３，５，６，および７では保管開始後７日目まで、２５個のサンプルのうち凍結が生じたものはなく、良好な過冷却状態が維持されていた。これに対してヘッドスペース有りとした例１，４では、保管開始後３日目で既に凍結が生じていた。
また表３の結果より、例９では、容器内の食品が水道水である場合に、庫内温度が−６℃と、この試験の条件における水の過冷却領域よりも低い温度に設定されていたため、ヘッドスペース無しで冷却温度が−３．５℃／ｈであっても、保管開始から１５時間後には既に凍結が生じたものがあった。それでも、ヘッドスペース有りである例８よりも、凍結の生じかたは少なかった。
一方、例１０は、例９と食品が異なるだけであるが、保管開始後３９時間までは過冷却状態が維持され、４８時間以降に凍結が生じたものがあった。これは、チーズの成分が水に溶出しているため凝固点降下が生じたものと考えられる。
【００３５】
（例１１〜１３）
前記例１０において、食品を次の通りに変更し、製造するサンプルの数を各１個ずつとした他は同様にして、恒温恒湿槽での保管を開始してから１５時間後、２４時間後、３９時間後、４８時間後、６３時間後、および８７時間後に凍結が生じたサンプルの数を調べた。これらの結果を表４に示す。
例１１：市販の牛乳（３．５牛乳（商品名）、森永乳業社製）２１０ｇ
例１２：生クリーム（フレッシュヘビー（商品名）、森永乳業社製）２１０ｇ
例１３：脱脂粉乳の８．７７質量％水溶液２１０ｇ
【００３６】
【表４】
表４の結果より、いずれの食品についても、良好な過冷却状態を安定して得ることができた。
【００３８】
（例１４〜１６）
まず、容器内に収容する食品として用いるモッツァレラチーズを製造した。すなわち、生乳を殺菌した後、３２〜３６℃に冷却し、乳酸菌を添加し、レンネットを添加して凝乳させ、得られたカード（凝乳）をカットし、生じたホエー（乳清）を適量除去し、残ったホエー中で発酵させた。ｐＨが４．９〜５．２に達したところで、カードをカットし、７２〜８２℃の熱湯中で練って弾力がある状態とした後、１００ｇずつ球状に成形して冷却した。得られたモッツァレラチーズを殺菌水１１０ｇとともにモッツァレラ用スタンディングパウチに充填し、ヘッドスペースが無いようにヒートシールした。
【００３９】
このようにして製造した直後のパウチ入りモッツァレラチーズ（品温２０℃）を下記表５に示す冷却速度で、それぞれ品温が−３．０℃になるまで冷却した。品温が−３．０℃になるまでに要する冷却時間を下記表５に合わせて示す。これにより、いずれのチーズも過冷却状態となった。
続いて、それぞれのチーズを、品温が−３．０℃に達した後、さらに４日間−３℃で保管した。そして、２〜５℃／ｈの昇温速度で＋１０℃まで昇温させ、＋１０℃で５週間保管したチーズを、５人のパネラーに試食してもらい、風味を評価した。また５週間保管後のチーズの外観を観察した。これらの結果を下記表５に示す。
【００４０】
（参考例）
参照用のサンプルとして、上記例１４と同様にして製造したパウチ入りモッツァレラチーズを製造直後から５週間、＋１０℃で保管した。
５週間保管後の製品の風味および外観を、上記例１４と同様にして評価した。その結果を下記表５に示す。
【００４１】
【表５】
表５の結果より、冷却速度を−５．０℃／ｈとした例１６では、＋１０℃で５週間保管した後も、外観および風味が良好であったのに対して、冷却速度が−０．５℃／ｈ以下と小さい例１４，１５では、外観的にはモッツァレラチーズにガスホールが発生し、風味が劣化した。これは、例１６では、冷却速度が速かったので、製造直後の製品が過冷却状態に達するまでの時間が短かく、初期段階での細菌（例えばヘテロ乳酸菌や雑菌）の増殖が抑えられたことにより、昇温後の細菌の増殖も効果的に抑えられたためと考えられる。
また参考例では、製造直後４週間後に、外観および風味の不良が確認されたことから、＋１０℃で４週間未満の保管が可能であったと認められる。
これに対して例１６では、＋１０℃に昇温後も５週間の保存が可能であり、比較的速い冷却速度で、一旦、過冷却状態とした例１６は、過冷却状態を経ない参考例より保存性に優れていることが認められた。
【００４３】
（例１７〜２０）
下記表６に示す条件で食品の保存を行った。すなわち ポリエチレンテレフタレートとポリエチレンをラミネートした複合材料からなる容器（パウチ、大日本印刷社製）に市販の牛乳（森永乳業社製）１００ｃｃを充填した。
これを▲１▼液面下でヘッドスペースが無い状態でヒートシールして密封したサンプル、または▲２▼容器内にヘッドスペースが有る状態でヒートシールしたサンプルをそれぞれ２５個作製した。
これを冷蔵庫内にて、牛乳の凍結点である−０．５℃付近を通過するときの冷却速度を▲１▼−５．０℃／ｈ、または▲２▼−１０．０℃／ｈとして、＋５℃から牛乳の過冷却領域である−７℃まで冷却した。品温が−７℃に達したとき、およびその後−７℃の冷蔵庫内で７日間保存したときに、２５個のサンプルのうち牛乳が凍結していたものの数を調べた。その結果を表６に示す。
【００４４】
【表６】
（例２１）
市販のモッツァレラチーズ（森永乳業社製）を５０ケース用意した。このモッツァレラチーズは、モッツァレラ用スタンディングパウチに１００ｇのモッツァレラチーズと１１０ｇの充填水がヘッドスペースが無いように収容されたもので、１ケースには１２個の製品が入っている。
品温１５℃のモッツァレラチーズをケースごと−３℃の冷蔵庫に２日保管して、品温を−２．５℃まで冷却した。０℃付近を通過するときの冷却速度は−０．６℃／ｈであった。これによりモッツァレラチーズは過冷却状態となった。
この後、−３℃のコンテナで２日間トラック輸送した。輸送先に到着したとき、品温は−３℃で、凍結したものは１個もなかった。
また、これを−３℃の冷蔵庫で７．５ヶ月間保管したところ、凍結したものは１個もなく、風味、物性等も保管前に比してほぼ同程度に維持されており、問題はなかった。
【００４６】
（例２２〜２３）
下記表７に示す条件で、例３，６，７と同様にして、モッツァレラチーズをヘッドスペース無しで容器内に収容し、所定の冷却温度で２５個を冷却した。ただし、この例２２および例２３においては、品温が−２℃以下になった時点で、容器に対し、１２０往復／分の条件で振動を与え続けた。
この結果、振動を与えつつ庫内温度−４℃で保管した例２２では、全てのサンプルが凍結しなかったが、振動を与えつつ庫内温度−５℃で保管した例２３では、いくつかのサンプルに凍結が生じていた。
なお、一般的に、例２２において同一のモッツァレラチーズを用いヘッドスペース有りとした場合は、例２２と同様の振動を与えると−４℃までの冷却・保管は不可能である。したがって、本発明によれば、従来技術に比して、振動、その他の刺激に対する耐性が強いことがうかがえる。
また、特にモッツァレラチーズの場合にあっては、表１に示すように好ましい過冷却領域は−０．３℃〜−５．０℃であるが、特に、冷却温度および／または保管温度が−４．０℃以上であれば振動の影響を受けにくく、好ましいことが判明した。
【００４７】
【表７】
【発明の効果】
以上説明したように本発明の食品の保存方法によれば、食品を、容器内にヘッドスペースが無いように収容した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て、該食品を過冷却状態とすることにより、短時間で安定性に優れた過冷却状態が得られ、食品の保存性を向上させることができる。
また本発明の食品の保存方法によれば、食品を、容器内にヘッドスペースが無いように収容した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て該食品を過冷却状態とした後、該過冷却状態を解除して凍結状態とすることにより、凍結障害を防止し、食品の品質を高度に維持しつつ冷凍保存することができる。
また本発明の未凍結水の製造方法によれば、水を、容器内にヘッドスペースが無いように充填した状態で、凍結点より高い温度から凍結点以下の温度まで−０．５℃／ｈを越え−５．０℃／ｈ以下の冷却速度で冷却する工程を経て、該水を過冷却状態とすることにより、簡単な工程で未凍結水を安価に製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for storing food in a supercooled state, a method for storing food in a frozen state, and a method for producing unfrozen water with water in a supercooled state.
[0002]
Problems to be solved by the prior art and the invention
It is a well-known fact that low-temperature storage as a method of preserving food is a commonly practiced method and an effective method. Low-temperature preservation techniques can be broadly divided into refrigeration and freezing, and it is well known that microbiologically, the lower the preservation temperature, the more advantageous.
However, the preservation method by freezing has a problem in that quality deterioration called freezing failure tends to occur such as generation of drip due to freezing, protein denaturation, and damage to flesh due to damage or deformation of cell tissues.
[0003]
By the way, when a food is cooled under a specific cooling condition, it is known that the food is not frozen even at a temperature below the freezing point of the food, that is, becomes a supercooled state. Storage has the advantage that cooling disturbances such as protein denaturation due to freezing and damage to cell tissues can be avoided.
[0004]
As a method for storing food in a supercooled state, for example, JP-A-5-161449 discloses that fruits and vegetables are sealed in a plastic bag having a thickness of 20 to 100 μm, and for 1 minute to 12 hours. After cooling to a temperature 1 to 2 ° C higher than the freezing point (freezing point) of the fruit / vegetable, supercooling destruction is performed at a very slow cooling rate of -0.5 ° C / hour to -0.5 / 24 hours. It describes a method of cooling to a temperature before the temperature and storing or transporting it as it is.
Japanese Patent Application Laid-Open No. Hei 8-2522082 discloses that food is rapidly cooled from room temperature to around a freezing point (freezing point), and then slowly cooled to 0.01 ° C./hour to 0.5 / hour. A method is described in which a supercooled state is achieved by cooling at a high cooling rate.
[0005]
However, these methods require slow cooling in order to bring the food into a supercooled state, so that the cooling process takes a long time, the processing capacity is low, and the growth of bacteria during the cooling process is sufficiently suppressed. There was a problem that it was difficult.
[0006]
In addition, the supercooled state is a state in which the liquid or vapor does not undergo transition and retains the original phase even when cooled below the phase transition temperature, and is a very unstable state. For this reason, the supercooled state is released very easily due to mixing of impurities, vibration, and temperature change, and the food is frozen, so that there is a problem that the method of preserving the food is not practical.
[0007]
Further, it is difficult to make water containing impurities such as tap water into a stable and unfrozen state below the freezing point, and JP-A-8-252082 discloses that raw water is filtered and / or filtered with a microfilter or the like. Alternatively, a method of producing unfrozen water through a step of removing impurities by distillation is described.
[0008]
However, when the step of removing impurities in the raw water is provided in this manner, there is a problem that the manufacturing process is complicated, the productivity is deteriorated, and the manufacturing cost is increased.
[0009]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method of preserving a food, which can bring a food into a supercooled state in a shorter time, and can stably maintain the supercooled state. .
Another object of the present invention is to provide a food preservation method capable of preserving food in a frozen state with little deterioration in quality.
Another object of the present invention is to provide a method for producing unfrozen water that can produce unfrozen water through simple steps at low cost.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on cooling conditions for bringing a food into a supercooled state, and as a result, by setting the food in a state where there is no head space in the container, conventionally, a supercooled state is obtained. That the food can be brought to a supercooled state without freezing even if cooled at a higher cooling rate than the slow cooling rate required for the food, and that there is no head space in the container in this way. It has been found that the food in the supercooled state at a higher cooling rate than before in the state of being housed therein has excellent stability in the supercooled state.
[0011]
That is, the method for storing food of the present invention is a method for storing food in a supercooled state, in a state where food is stored in a container without a headspace, from a temperature higher than the freezing point to a temperature below the freezing point. The food is brought into a supercooled state through a step of cooling at a cooling rate of more than -0.5 ° C / h to -5.0 ° C / h or less to a temperature. The container is preferably made of a material containing a plastic, particularly a material containing at least one selected from the group consisting of nylon, polyethylene, polystyrene, polypropylene, and polyethylene terephthalate.
[0012]
Further, the present inventors have further studied, as a result of the food of the supercooled state by the method of the present invention, when the supercooled state is released by forcibly stimulating the food, the food freezes rapidly, and It has been found that the frozen state obtained in this way causes less damage to cell tissues and extremely low quality deterioration as compared with the conventional rapid freezing method in which the frozen state passes through a supercooled state.
[0013]
That is, the food preservation method of the present invention is a method of preserving food in a frozen state, and in a state where the food is stored without a head space in a container, a temperature from a temperature higher than the freezing point to a temperature below the freezing point. After the food is put into a supercooled state through a step of cooling at a cooling rate of more than -0.5 ° C / h to -5.0 ° C / h or less, the supercooled state is released to a frozen state. It is characterized by.
[0014]
In order to release the supercooled state, it is preferable to perform cooling at a cooling rate of −15 ° C./h or more.
[0015]
Further, according to the method of the present invention, water can be easily and stably supercooled.
That is, in the method for producing unfrozen water of the present invention, in a state where water is filled so that there is no head space in the container, the temperature exceeds -0.5 ° C / h from a temperature higher than the freezing point to a temperature lower than the freezing point. The method is characterized in that the water is converted into unfrozen water through a step of cooling at a cooling rate of −5.0 ° C./h or less.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail. First, a method of storing food in a supercooled state as a first embodiment of the present invention will be described.
In the present embodiment, first, the food is housed in a container and sealed. At this time, there is no head space (gas phase) in the container.
The food is not particularly limited, and various liquid, pasty, and solid foods are applicable. For example, drinking water, raw material water, milk, other drinks, cream, condensed milk, yogurt, cheese, other dairy products, fruits, vegetables, meat, seafood, various processed foods, and the like are included.
When the food is in a liquid or paste form, the head space can be easily eliminated by filling the container with the food and sealing it below the liquid level. On the other hand, when the food is solid, the food is contained in a container, and, for example, water, a solution, and a liquid that does not adversely affect the quality of the food such as milk is filled and sealed below the liquid surface, so that the head space is reduced. Can be eliminated.
[0017]
As for the container, for example, a plastic film or a flexible material such as a composite material including a plastic film can more stably obtain a supercooled state than a hard material such as stainless steel or glass. It is preferred. For example, in the case of the mozzarella cheese in the examples described later, the mozzarella cheese described in the example is filled in a stainless steel can (no head space), and if the same cooling as in the example is performed, the probability of freezing is reduced in each example. Higher than that.
A preferred container material is a material containing a plastic, and is a composite material obtained by combining any plastic material selected from nylon, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, and the like, or a laminate of two or more plastic materials selected from these materials. And a composite material obtained by combining one or more plastic materials selected from these materials with other materials such as paper. When a plastic material is combined with another material, the inner surface of the container (that is, the surface in contact with the food) is preferably formed of a plastic material. Although the shape of the container is not particularly limited, it can be, for example, a bag shape, a spherical shape, a tube shape, a standing pouch shape, or the like, and it is preferable that the shape be as spherical as possible.
[0018]
Next, the food stored in the container is cooled, and the temperature of the food is reduced to a supercooling region where the food enters a supercooled state. The cooling conditions are as follows: in the process of lowering the temperature of the food, at least the cooling rate when passing through the freezing point is in the range of more than -0.5 ° C / h to -5.0 ° C / h or less, ie, -0.5 The speed is set so as to be faster than −5.0 ° C./h or −5.0 ° C./h or lower.
If the cooling rate at the time of passing through the freezing point is lower than the above range, the effect of suppressing the growth of bacteria cannot be sufficiently obtained, and the processing efficiency will be poor. If the cooling rate is higher than the above range, a supercooled state may not be obtained.
[0019]
When a solid food and a liquid for eliminating the head space are contained in the container, both the food and the liquid are cooled to a temperature at which both the food and the liquid are in a supercooled state. In this case, the cooling conditions are such that in the process of lowering the temperature of the food and the liquid, both the cooling rate when passing through the freezing point of the food and the cooling rate when passing through the freezing point of the liquid are -0.5. The temperature is set so as to be in the range of more than C / h and not more than -5.0 C / h.
The cooling may be performed in a single step at a constant cooling rate of from -0.5 ° C / h to -5.0 ° C / h or less from the start of cooling to a desired supercooling region, or From the start of cooling to the vicinity of the freezing point, the first cooling is performed at a cooling rate exceeding -5.0 ° C / h, and then the cooling rate is increased from -0.5 ° C / h to -5.0 ° C / h or less. And the second cooling may be performed to a supercooled region below the freezing point.
During cooling, it is preferable that the container containing the food be kept stationary. For example, it is preferable to perform cooling by standing and storing a container containing food in a refrigerator set to a predetermined temperature, a set temperature in the refrigerator, a flow rate of cold air in the refrigerator, a method of hitting cold air, The cooling rate can be controlled by changing the effective volume in the refrigerator.
[0020]
By maintaining the temperature of the supercooled food in the supercooled region together with the container in the supercooled state in this way, the food can be stored in the supercooled state.
The freezing point of the food and the temperature zone of the supercooled region are substantially determined for each individual food, and the temperature zone of the supercooled region is a temperature range from the freezing point to a temperature -20 ° C lower than the freezing point in principle. . Table 1 below shows examples of the freezing point and those having a particularly preferable range of the supercooling region.
[0021]
[Table 1]
According to this embodiment, in the process of lowering the food temperature, the food passes through the freezing point at a faster cooling rate of more than -0.5 ° C / h and less than -5.0 ° C / h than before. As a result, the food can be supercooled in a shorter time than before. Therefore, the time required for the cooling step can be reduced, and the processing capacity can be improved.
In addition, conventional cooling equipment can be used as equipment, and it is not necessary to provide new equipment. In addition, since it does not add food to the food or apply pressure to obtain a supercooled state, there is no risk of impairing the flavor of the food, and it is suitable for milk drinks and dairy products, etc., where the flavor is easy to change Can also be applied.
[0023]
In addition, since the manufactured food can be brought into a supercooled state in a shorter time, it is possible to effectively suppress the growth of bacteria in the initial stage after the manufacturing. Therefore, it is particularly suitable for storage of milk drinks, dairy products, and the like, in which bacteria are relatively easy to grow, and the storage stability can be improved.
In addition, in a state where the food is stored in the container without a head space and cooled at a relatively high cooling rate, the supercooled state is not easily destroyed, and the supercooled state is not easily destroyed. The cooling state can be maintained. Therefore, even if vibration is applied, it is hard to be in a frozen state, so that it is possible to transport in a temperature zone of a supercooled region, and to maintain a good supercooled state even after transport.
[0024]
Next, a method for storing food in a frozen state as a second embodiment of the present invention will be described.
In the present embodiment, first, as in the first embodiment, in a state where the food is accommodated in the container such that there is no head space, at least the cooling rate when passing through the freezing point is -0.5 ° C. The temperature of the food is lowered to a supercooling region under cooling conditions exceeding / h and within a range of -5.0 ° C / h or less.
Next, the supercooled state is released by forcibly applying a stimulus to the food in the supercooled state in this way, and the food is frozen. Specifically, it is preferable to cool the superconducting food in a container at a cooling rate of −15 ° C./h or more. If the cooling rate at this time is lower than −15 ° C./h, there is a possibility that destruction of cell tissues and denaturation of proteins may occur during the freezing process.
[0025]
By keeping the food in the frozen state in this way at a temperature lower than the freezing point of the whole container, the food can be stored in a frozen state.
[0026]
According to the present embodiment, similarly to the first embodiment, after a supercooled state in which moisture is not frozen at a temperature below the freezing point and then freezing rapidly, a frozen state with less refrigeration failure is performed. Can be obtained. This is because the freezing of the intracellular fluid and extracellular fluid from a state in which the intracellular fluid and extracellular fluid are not frozen in a supercooled state causes the transfer of free water from the intracellular fluid to the extracellular fluid during the freezing process, It is considered that is easy to freeze because it is diluted, and the intracellular solution is concentrated and hard to freeze. As a result, only the intracellular solution is unfrozen and the others are frozen. Further, in the case of a food containing a protein, ice crystals are reduced by rapid freezing, so that the tertiary structure of the protein is less likely to be destroyed by the ice crystals, and denaturation of the protein is suppressed.
In addition, since the food is cooled to the supercooled region in a relatively short time, it is possible to effectively suppress the growth of bacteria in the initial stage after the production and improve the preservability.
[0027]
The method of the present embodiment can be applied to various foods similarly to the first embodiment, and can be frozen and preserved while preventing refrigeration and maintaining high quality. In particular, fruits and vegetables, which were conventionally considered to be easily affected by freezing, and dairy products having a relatively high moisture content are also preferable because quality deterioration due to cryopreservation and thawing can be prevented.
[0028]
For example, in the conventional freezing technology, the focus of technology development was how fast it can be frozen, and the ice crystals can be atomized by passing through the so-called maximum ice crystal formation zone in a short time, but this method alone had limitations. . That is, for example, naturally soft fruits such as strawberries and moist dairy products such as mozzarella cheese, cream cheese, etc., no matter how fast they freeze, the tissue is destroyed by freezing, water separation occurs and the commercial value is lost. That was inevitable.
On the other hand, according to the method of the present embodiment, for example, even in foods such as vegetables, fruits, and dairy products that are liable to cause freezing trouble, it is possible to prevent tissue destruction during the freezing process and the thawing process. The previous tissue state can be maintained.
[0029]
Next, a method for producing unfrozen water will be described as a third embodiment of the present invention.
In the present embodiment, first, water is accommodated in a container and sealed, as in the first embodiment. At this time, there is no head space (gas phase) in the container.
The composition of the water is not particularly limited. Ordinary tap water may be used, or may be subjected to sterilization treatment, impurity removal treatment, or the like. The same container as in the first embodiment can be used as the container.
Next, the container filled with water is cooled, and the cooling rate at least when passing through the freezing point exceeds −0.5 ° C./h and is −5.0 ° C./h, as in the first embodiment. Uncooled water is obtained at a temperature below the freezing point by lowering the temperature of the water to a supercooled region under cooling conditions within the range of h or less.
[0030]
According to the present embodiment, even if the water contains impurities such as tap water, it can be easily brought into the supercooled state only through the cooling step, so that the unfrozen water can be produced with good productivity and at low cost. Can be manufactured.
[0031]
【Example】
Hereinafter, the effects of the present invention will be clarified by showing specific examples.
(Examples 1 to 10)
Under the conditions shown in Tables 2 and 3 below, the food was accommodated in a container and cooled at a predetermined cooling rate.
That is, as the container, a container (manufactured by Dai Nippon Printing Co., Ltd.) having a size of 13.0 cm × 14.5 cm, made of a laminate of nylon / polyethylene, was used.
This container was filled with (1) 210 g of tap water or (2) 100 g of mozzarella cheese and 110 g of filling water (described as M cheese in the table).
This was sealed by heat sealing with no headspace below the liquid surface (no headspace), or (2) After heat sealing with no headspace, air was injected into the container using a syringe. Injected (with headspace).
In this manner, 25 samples each of which the food was filled in the container were prepared, and these were left in a constant temperature room at 20 ° C. until the product temperature in the container reached 20 ° C. The sample was stored in a constant temperature and humidity chamber (LH40-03M: trade name, Nagano Kagaku Kikai Seisakusho).
In the process of lowering the temperature of the food in the container, the cooling rates when passing near 0 ° C. are (1) -3.4 ° C./h, (2) -1.9 ° C./h, and (3). -5.0 ° C / h or (4) -3.5 ° C / h. Note that the cooling rate does not always correlate with the temperature in the refrigerator, and varies depending on the flow rate of the cool air in the refrigerator, how the cool air is hit, and the effective volume in the refrigerator.
In Examples 1 to 7, on and after the third day from the start of storage in the thermo-hygrostat, the number of frozen samples was checked every day. In Examples 8 to 10, the number of samples that had been frozen 15 hours, 24 hours, 39 hours, 48 hours, 63 hours, and 87 hours after the start of storage in the thermo-hygrostat was determined. Examined. The results are shown in Tables 2 and 3.
[0032]
[Table 2]
[Table 3]
According to the results in Table 2, in Examples 2, 3, 5, 6, and 7, in which there was no headspace, no freezing occurred among the 25 samples until the 7th day from the start of storage, and a good supercooled state was obtained. Was maintained. On the other hand, in Examples 1 and 4 in which the head space was provided, the freezing had already occurred on the third day after the start of storage.
Further, from the results in Table 3, in Example 9, when the food in the container is tap water, the temperature in the refrigerator is set to -6 ° C, which is lower than the supercooling region of water under the conditions of this test. Therefore, even if the cooling temperature was -3.5 ° C / h without a headspace, some of the materials had already been frozen 15 hours after the start of storage. Still, there was less freezing than in Example 8 with headspace.
On the other hand, Example 10 was different from Example 9 only in food, but the supercooled state was maintained until 39 hours after the start of storage, and there was a case where freezing occurred after 48 hours. This is presumably because the components of the cheese were eluted in the water and the freezing point was lowered.
[0035]
(Examples 11 to 13)
In the same manner as in Example 10, except that the food was changed as follows, and the number of samples to be manufactured was changed to one each, 15 hours after starting storage in the thermo-hygrostat, and 24 hours after After, 39 hours, 48 hours, 63 hours, and 87 hours, the number of samples in which freezing occurred was determined. Table 4 shows the results.
Example 11: 210 g of commercially available milk (3.5 milk (trade name), manufactured by Morinaga Milk Industry Co., Ltd.)
Example 12: 210 g of fresh cream (fresh heavy (trade name), manufactured by Morinaga Milk Products Co., Ltd.)
Example 13: 210 g of an 8.77% by mass aqueous solution of skim milk powder
[0036]
[Table 4]
From the results in Table 4, a good supercooled state could be stably obtained for all the foods.
[0038]
(Examples 14 to 16)
First, mozzarella cheese used as food stored in a container was manufactured. That is, after sterilizing raw milk, it is cooled to 32 to 36 ° C., lactic acid bacteria are added, rennet is added, and the curd is curd. The resulting curd (curd) is cut, and the resulting whey (whey) is produced. Was removed and fermented in the remaining whey. When the pH reached 4.9 to 5.2, the curd was cut, kneaded in hot water at 72 to 82 ° C to make it elastic, and then molded into 100 g spherical shapes and cooled. The obtained mozzarella cheese was filled into a standing pouch for mozzarella together with 110 g of sterilized water, and heat-sealed so that there was no head space.
[0039]
The pouch-containing mozzarella cheese (product temperature 20 ° C.) immediately after being manufactured in this manner was cooled at a cooling rate shown in Table 5 below until the product temperature reached −3.0 ° C. The cooling time required until the product temperature reaches -3.0 ° C is shown in Table 5 below. Thereby, all the cheeses were in a supercooled state.
Subsequently, each cheese was stored at −3 ° C. for another 4 days after the product temperature reached −3.0 ° C. Then, the temperature was raised to + 10 ° C. at a temperature rising rate of 2 to 5 ° C./h, and the cheese stored at + 10 ° C. for 5 weeks was tasted by five panelists, and the flavor was evaluated. The appearance of the cheese after storage for 5 weeks was observed. The results are shown in Table 5 below.
[0040]
(Reference example)
As a reference sample, the pouched mozzarella cheese produced in the same manner as in Example 14 was stored at + 10 ° C. for 5 weeks immediately after production.
The flavor and appearance of the product after storage for 5 weeks were evaluated in the same manner as in Example 14 above. The results are shown in Table 5 below.
[0041]
[Table 5]
From the results in Table 5, in Example 16 in which the cooling rate was −5.0 ° C./h, the appearance and flavor were good even after storage at + 10 ° C. for 5 weeks, whereas the cooling rate was −0. In Examples 14 and 15 as small as 0.5 ° C./h or less, gas holes were generated in the mozzarella cheese in appearance, and the flavor was deteriorated. This is because, in Example 16, since the cooling rate was high, the time required for the product immediately after production to reach the supercooled state was short, and the growth of bacteria (eg, heterolactic bacteria and various germs) in the initial stage was suppressed. It is thought that the growth of the bacteria after the temperature increase was also effectively suppressed.
In the reference example, poor appearance and flavor were confirmed 4 weeks after the production, indicating that storage at + 10 ° C. for less than 4 weeks was possible.
On the other hand, in Example 16, storage for 5 weeks was possible even after the temperature was raised to + 10 ° C., and Example 16 in which the supercooling was performed once at a relatively high cooling rate was a reference example in which no supercooling was performed. It was confirmed that the composition was more excellent in preservability.
[0043]
(Examples 17 to 20)
The food was stored under the conditions shown in Table 6 below. That is, a container (pouch, manufactured by Dai Nippon Printing Co., Ltd.) made of a composite material obtained by laminating polyethylene terephthalate and polyethylene was filled with 100 cc of commercially available milk (manufactured by Morinaga Milk Industry Co., Ltd.).
Twenty-five samples each of which were heat-sealed with (1) a head space below the liquid level and no head space, or (2) heat-sealed with a head space inside the container.
In the refrigerator, the cooling rate when passing around the freezing point of milk -0.5 ° C is defined as (1) -5.0 ° C / h or (2) -10.0 ° C / h. , + 5 ° C to -7 ° C, a supercooled region of milk. When the product temperature reached -7 ° C, and then stored in a refrigerator at -7 ° C for 7 days, the number of milk samples frozen out of 25 samples was determined. Table 6 shows the results.
[0044]
[Table 6]
(Example 21)
Fifty cases of commercially available mozzarella cheese (manufactured by Morinaga Milk Products Co., Ltd.) were prepared. This mozzarella cheese is a mozzarella standing pouch in which 100 g of mozzarella cheese and 110 g of filling water are accommodated without a head space, and one case contains 12 products.
The mozzarella cheese at a product temperature of 15 ° C was stored together with the case in a refrigerator at -3 ° C for 2 days, and the product temperature was cooled to -2.5 ° C. The cooling rate when passing around 0 ° C. was −0.6 ° C./h. This put the mozzarella cheese in a supercooled state.
Thereafter, they were transported by truck in a container at −3 ° C. for 2 days. When we arrived at the destination, the temperature was -3 ° C and none of them were frozen.
Further, when this was stored in a refrigerator at -3 ° C. for 7.5 months, there was no frozen one, and the flavor, physical properties, etc. were maintained at about the same level as before storage, and the problem was that Did not.
[0046]
(Examples 22 to 23)
Under the conditions shown in Table 7 below, in the same manner as in Examples 3, 6, and 7, mozzarella cheese was stored in a container without a head space, and 25 pieces were cooled at a predetermined cooling temperature. However, in Examples 22 and 23, when the product temperature became −2 ° C. or less, the container was continuously vibrated under the condition of 120 reciprocations / minute.
As a result, in Example 22 in which the sample was stored at a temperature of −4 ° C. while applying vibration, all the samples did not freeze, but in Example 23 in which the sample was stored at a temperature of −5 ° C. while applying vibration, some samples were not frozen. The sample had frozen.
In addition, in general, when the same mozzarella cheese is used and a head space is provided in Example 22, if the same vibration as in Example 22 is applied, cooling and storage to −4 ° C. cannot be performed. Therefore, according to the present invention, it can be seen that the resistance to vibration and other stimuli is stronger than that of the related art.
In addition, particularly in the case of mozzarella cheese, the preferable supercooling region is -0.3 ° C to -5.0 ° C as shown in Table 1, but the cooling temperature and / or the storage temperature are particularly −4 ° C. It was found that when the temperature was 0.0 ° C. or more, it was hard to be affected by vibration, which was preferable.
[0047]
[Table 7]
【The invention's effect】
As described above, according to the method for storing food of the present invention, in a state where the food is stored without a head space in the container, from the temperature above the freezing point to the temperature below the freezing point -0.5 ° C. / H through a step of cooling at a cooling rate of not more than /5.0°C/h or less, and by supercooling the food, a supercooled state with excellent stability can be obtained in a short time, Preservability can be improved.
Further, according to the food preservation method of the present invention, in a state where the food is accommodated in the container such that there is no head space, the temperature exceeds -0.5 ° C / h from a temperature higher than the freezing point to a temperature below the freezing point. After passing the food in a supercooled state through a step of cooling at a cooling rate of −5.0 ° C./h or less, the supercooled state is released to a frozen state, thereby preventing freezing failure and preventing the food from being frozen. It can be stored frozen while maintaining high quality.
Further, according to the method for producing unfrozen water of the present invention, in a state where water is filled so that there is no head space in the container, the temperature is -0.5 ° C / h from a temperature higher than the freezing point to a temperature lower than the freezing point. By passing the water in a supercooled state through a step of cooling at a cooling rate of -5.0 ° C./h or less, unfrozen water can be produced in a simple process at low cost.
Claims (5)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001380369A JP3592668B2 (en) | 2001-12-13 | 2001-12-13 | Food preservation method and unfrozen water production method |
| ES02788662T ES2283622T3 (en) | 2001-12-13 | 2002-11-26 | METHOD FOR CONSERVING FOOD AND METHOD FOR PRODUCING UNFROZEN WATER. |
| US10/492,306 US7524521B2 (en) | 2001-12-13 | 2002-11-26 | Method of preserving food in a supercooled state |
| AU2002355039A AU2002355039B2 (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| CNB028215303A CN100372484C (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| NZ532192A NZ532192A (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| KR1020047006252A KR100560001B1 (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| EP02788662A EP1454541B1 (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| AT02788662T ATE354976T1 (en) | 2001-12-13 | 2002-11-26 | METHOD FOR PRESERVING FOOD AND METHOD FOR PRODUCING NON-FROZEN WATER |
| CA002465863A CA2465863C (en) | 2001-12-13 | 2002-11-26 | Method of preserving food and method of producing unfrozen water |
| DK02788662T DK1454541T3 (en) | 2001-12-13 | 2002-11-26 | Process for preserving food and method for producing frozen water |
| PCT/JP2002/012322 WO2003049557A1 (en) | 2001-12-13 | 2002-11-26 | Method of preserving food, and method of producing non-frozen water |
| DE60218523T DE60218523T2 (en) | 2001-12-13 | 2002-11-26 | METHOD FOR PRESERVING FOOD, AND METHOD FOR PRODUCING UNFROOF WATER |
| NO20041798A NO325542B1 (en) | 2001-12-13 | 2004-04-30 | Process for preserving foods and process for preparing frozen water |
| HK05100217A HK1068002A1 (en) | 2001-12-13 | 2005-01-11 | Method of presreving food, and method of producingnon-frozen water |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001380369A JP3592668B2 (en) | 2001-12-13 | 2001-12-13 | Food preservation method and unfrozen water production method |
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| JP2003180314A JP2003180314A (en) | 2003-07-02 |
| JP3592668B2 true JP3592668B2 (en) | 2004-11-24 |
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| US (1) | US7524521B2 (en) |
| EP (1) | EP1454541B1 (en) |
| JP (1) | JP3592668B2 (en) |
| KR (1) | KR100560001B1 (en) |
| CN (1) | CN100372484C (en) |
| AT (1) | ATE354976T1 (en) |
| AU (1) | AU2002355039B2 (en) |
| CA (1) | CA2465863C (en) |
| DE (1) | DE60218523T2 (en) |
| DK (1) | DK1454541T3 (en) |
| ES (1) | ES2283622T3 (en) |
| HK (1) | HK1068002A1 (en) |
| NO (1) | NO325542B1 (en) |
| NZ (1) | NZ532192A (en) |
| WO (1) | WO2003049557A1 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4940410B2 (en) * | 2005-12-19 | 2012-05-30 | アップル インコーポレイテッド | User-to-user recommender |
| US7743009B2 (en) * | 2006-02-10 | 2010-06-22 | Strands, Inc. | System and methods for prioritizing mobile media player files |
| US7824725B2 (en) | 2007-03-30 | 2010-11-02 | The Coca-Cola Company | Methods for extending the shelf life of partially solidified flowable compositions |
| WO2008121557A1 (en) * | 2007-03-30 | 2008-10-09 | The Coca-Cola Company | Methods for extending the shelf life of partially solidified flowable compositions |
| US20100083687A1 (en) * | 2007-04-17 | 2010-04-08 | Mitsubishi Electric Corporation | Refrigerator and frozen food preservation method |
| JP4827788B2 (en) * | 2007-04-17 | 2011-11-30 | 三菱電機株式会社 | refrigerator |
| JP4775340B2 (en) * | 2007-07-20 | 2011-09-21 | 三菱電機株式会社 | refrigerator |
| JP2009044981A (en) * | 2007-08-17 | 2009-03-05 | Mitsubishi Electric Corp | Freezing method and freezing apparatus |
| KR101330449B1 (en) * | 2007-09-14 | 2013-11-15 | 엘지전자 주식회사 | Supercooling method and supercooling apparatus |
| JP2009165392A (en) * | 2008-01-15 | 2009-07-30 | Toyo Seikan Kaisha Ltd | Frozen material packaged in plastic container, and method for producing the same |
| JP5203760B2 (en) * | 2008-03-21 | 2013-06-05 | 株式会社東芝 | refrigerator |
| KR20110000836A (en) | 2009-06-29 | 2011-01-06 | 삼성전자주식회사 | Refrigerating apparatus and method for controlling the same |
| DK2594137T3 (en) * | 2011-09-20 | 2014-12-01 | Oriental Yeast Co Ltd | Frozen whip cream, manufacturing method thereof, cream and manufacturing method thereof |
| US20140272017A1 (en) * | 2013-03-15 | 2014-09-18 | Cyrus A. SEPEHR | Consumer oriented system for delivery of product including single-serving package for preservative-free frozen fruit pieces |
| JP6832585B2 (en) * | 2015-05-28 | 2021-02-24 | ルセット・ナイン株式会社 | Freezing method of milk or dairy products |
| JP2017081138A (en) * | 2015-10-30 | 2017-05-18 | 京セラドキュメントソリューションズ株式会社 | Image formation apparatus and print job management program |
| CN107751713A (en) * | 2016-08-22 | 2018-03-06 | 九阳股份有限公司 | A kind of food nutrition freezing method |
| CN110906683A (en) * | 2019-10-30 | 2020-03-24 | 合肥晶弘电器有限公司 | Instant freezing storage control method and refrigerator |
| CN110953823A (en) * | 2019-10-30 | 2020-04-03 | 合肥晶弘电器有限公司 | Control method for instant freezing storage of refrigerator and refrigerator |
| CN110953832A (en) * | 2019-10-30 | 2020-04-03 | 合肥晶弘电器有限公司 | Refrigerator instant freezing storage control method and refrigerator |
| CN110953833A (en) * | 2019-10-30 | 2020-04-03 | 合肥晶弘电器有限公司 | Refrigerator instant freezing storage control method and refrigerator |
| CN110953825A (en) * | 2019-10-30 | 2020-04-03 | 合肥晶弘电器有限公司 | Control method for instant freezing storage of refrigerator and refrigerator |
| CN110701858A (en) * | 2019-10-30 | 2020-01-17 | 合肥晶弘电器有限公司 | Instant freezing storage control method and refrigerator |
| CN110986456A (en) * | 2019-10-30 | 2020-04-10 | 合肥晶弘电器有限公司 | Instant freezing control method for refrigeration equipment and refrigeration equipment |
| CN110701860A (en) * | 2019-10-30 | 2020-01-17 | 合肥晶弘电器有限公司 | Instant freezing chamber control method and refrigerator |
| CN112205563A (en) * | 2020-09-28 | 2021-01-12 | 中国科学院广州能源研究所 | Super-ice-temperature quick-frozen food fresh-keeping method |
| RU2767205C1 (en) * | 2022-01-13 | 2022-03-16 | Общество с ограниченной ответственностью «КЬЮМИ» | Method for preparing semi-finished products in a package with the possibility of their further automated heating and/or cooking |
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| JPS56117065A (en) * | 1980-02-16 | 1981-09-14 | Hoshino Hiroshi | Rapid cooling device |
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| JPS6291170A (en) * | 1985-06-05 | 1987-04-25 | Jipukomu Kk | Method for freezing and preservation of food |
| JPS62201565A (en) * | 1985-10-31 | 1987-09-05 | Jipukomu Kk | Method for putting large-sized food in cold storage |
| JPS6391170A (en) | 1986-10-06 | 1988-04-21 | Fuji Photo Film Co Ltd | Coating method |
| JPS63254945A (en) | 1987-04-10 | 1988-10-21 | Showa Denko Kk | Freezing of food |
| US4832972A (en) * | 1988-04-06 | 1989-05-23 | Cornell Research Foundation, Inc. | Process for preservation of fish |
| JP2515157B2 (en) | 1989-07-14 | 1996-07-10 | 株式会社氷温 | Cold storage method of fresh food |
| JPH04252171A (en) * | 1990-12-26 | 1992-09-08 | Oozeki Kk | Alcoholic drink freezable by pouring |
| JPH04299965A (en) * | 1991-03-29 | 1992-10-23 | Oozeki Kk | Soft drinks frozen in pouring |
| JPH0799991B2 (en) | 1991-12-17 | 1995-11-01 | 株式会社氷温 | Pre-cooling method for storage and transportation of fruits and vegetables |
| JPH06303954A (en) * | 1993-04-21 | 1994-11-01 | Japan Steel Works Ltd:The | Method for preserving food at low temperature |
| JP3787171B2 (en) | 1995-03-15 | 2006-06-21 | 株式会社氷温 | Non-freezing preservation method of foods etc. in temperature zone below freezing point |
| PT876183E (en) * | 1995-11-20 | 2002-11-29 | Unilever Nv | A PROCESS FOR OVERFLOWING |
| JPH09252739A (en) * | 1996-03-25 | 1997-09-30 | Nakano Vinegar Co Ltd | Production of bean curd-like food and bean curd-like frozen food |
| JPH10171353A (en) * | 1996-12-13 | 1998-06-26 | Katsuta Kimio | Supercooling history display implement, super-high-temperature history display implement, supercooling and super-high-temperature history display implement |
| US6305178B1 (en) * | 1999-05-06 | 2001-10-23 | Yuping Shi | Continuous system of freeze concentration for aqueous solutions |
| JP2001086967A (en) | 1999-09-22 | 2001-04-03 | Airtech Japan Ltd | Method for freezing and freezer using variance of magnetic field or electric field |
| US7059140B2 (en) * | 2001-12-12 | 2006-06-13 | John Zevlakis | Liquid milk freeze/thaw apparatus and method |
-
2001
- 2001-12-13 JP JP2001380369A patent/JP3592668B2/en not_active Expired - Fee Related
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2002
- 2002-11-26 AT AT02788662T patent/ATE354976T1/en active
- 2002-11-26 NZ NZ532192A patent/NZ532192A/en not_active IP Right Cessation
- 2002-11-26 AU AU2002355039A patent/AU2002355039B2/en not_active Ceased
- 2002-11-26 ES ES02788662T patent/ES2283622T3/en not_active Expired - Lifetime
- 2002-11-26 DE DE60218523T patent/DE60218523T2/en not_active Expired - Lifetime
- 2002-11-26 EP EP02788662A patent/EP1454541B1/en not_active Expired - Lifetime
- 2002-11-26 WO PCT/JP2002/012322 patent/WO2003049557A1/en active IP Right Grant
- 2002-11-26 CN CNB028215303A patent/CN100372484C/en not_active Expired - Fee Related
- 2002-11-26 CA CA002465863A patent/CA2465863C/en not_active Expired - Fee Related
- 2002-11-26 KR KR1020047006252A patent/KR100560001B1/en not_active IP Right Cessation
- 2002-11-26 DK DK02788662T patent/DK1454541T3/en active
- 2002-11-26 US US10/492,306 patent/US7524521B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100560001B1 (en) | 2006-03-13 |
| HK1068002A1 (en) | 2005-04-22 |
| CA2465863C (en) | 2009-08-04 |
| AU2002355039B2 (en) | 2007-05-17 |
| KR20050044331A (en) | 2005-05-12 |
| US20050003057A1 (en) | 2005-01-06 |
| NZ532192A (en) | 2005-07-29 |
| NO325542B1 (en) | 2008-06-16 |
| EP1454541A4 (en) | 2005-10-19 |
| ES2283622T3 (en) | 2007-11-01 |
| ATE354976T1 (en) | 2006-03-15 |
| JP2003180314A (en) | 2003-07-02 |
| NO20041798L (en) | 2004-04-30 |
| AU2002355039A1 (en) | 2003-06-23 |
| DE60218523T2 (en) | 2007-11-15 |
| DK1454541T3 (en) | 2007-06-04 |
| DE60218523D1 (en) | 2007-04-12 |
| CN100372484C (en) | 2008-03-05 |
| CN1578630A (en) | 2005-02-09 |
| CA2465863A1 (en) | 2003-06-19 |
| US7524521B2 (en) | 2009-04-28 |
| EP1454541A1 (en) | 2004-09-08 |
| WO2003049557A1 (en) | 2003-06-19 |
| EP1454541B1 (en) | 2007-02-28 |
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